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Materials with tunable negative electromagnetic performance, i.e., where dielectric permittivity becomes negative, have long been pursued in materials research due to their peculiar electromagnetic (EM) characteristics. Here, this promising feature is reported in materials on the case of plasma-synthesized nitrogen-doped graphene sheets with tunable permittivity over a wide (1-40 GHz) frequency range. Selectively incorporated nitrogen atoms in a graphene scaffold tailor the electronic structure in a way that provides an ultra-low energy (0.5-2 eV) 2D surface plasmon excitation, leading to subunitary and negative dielectric constant values in the Ka-band, from 30 up to 40 GHz. By allowing the tailoring of structures at atomic scale, this novel plasma-based approach creates a new paradigm for designing 2D nanomaterials like nanocarbons with controllable and tunable permittivity, opening a path to the next generation of 2D metamaterials., (© 2024 The Authors. Small published by Wiley‐VCH GmbH.)

Two samples of spent tire rubber (rubber A and rubber B) were submitted to thermochemical conversion by pyrolysis process. A450, B450 and A900, B900 chars were obtained from rubber A and rubber B at 450 °C and 900 °C, respectively. The chars were then applied as recovery agents of Nd 3+ and Dy 3+ from aqueous solutions in mono and bicomponent solutions, and their performance was benchmarked with a commercial activated carbon. The chars obtained at 900 °C were the most efficient adsorbents for both elements with uptake capacities around 30 mg g -1 . The chars obtained at 450 °C presented uptake capacities similar to the commercial carbon (≈ 11 mg g -1 ). A900 and B900 chars presented a higher availability of Zn ions that favored the ion exchange mechanism. It was found that Nd 3+ and Dy 3+ were adsorbed as oxides after Zn was released from silicate structures (Zn 2 SiO 4 ). A900 char was further selected to be tested with Nd/Dy binary mixtures and it was found a trend to adsorb a slightly higher amount of Dy 3+ due to its smaller ionic radius. The uptake capacity in bicomponent solutions was generally higher than for single component solutions due to the higher driving force triggered by the higher concentration gradient., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Because of the global necessity to decrease CO 2 emissions, biomass-based fuels have become an interesting option to explore; although, bio-oils need to be upgraded, for example, by catalytic hydrodeoxygenation (HDO), to reduce oxygen content. This reaction generally requires bifunctional catalysts with both metal and acid sites. For that purpose, Pt-Al 2 O 3 and Ni-Al 2 O 3 catalysts containing heteropolyacids (HPA) were prepared. HPAs were added by two different methods: the impregnation of a H 3 PW 12 O 40 solution onto the support and a physical mixture of the support with Cs 2.5 H 0.5 PW 12 O 40 . The catalysts were characterized by powder X-ray diffraction, Infrared, UV-Vis, Raman, X-ray photoelectron spectroscopy and NH 3 -TPD experiments. The presence of H 3 PW 12 O 40 was confirmed by Raman, UV-Vis and X-ray photoelectron spectroscopy, while the presence of Cs 2.5 H 0.5 PW 12 O 40 was confirmed by all of the techniques. However, HPW was shown to strongly interact with the supports, especially in the case of Pt-Al 2 O 3 . These catalysts were tested in the HDO of guaiacol, at 300 °C, under H 2 and at atmospheric pressure. Ni-based catalysts led to higher conversion and selectivity to deoxygenated compound values, such as benzene. This is attributed to both a higher metal and acidic contents of these catalysts. Among all tested catalysts, HPW/Ni-Al 2 O 3 was shown to be the most promising, although it suffered a more severe deactivation with time-on-stream.

The antibacterial properties of cellulose acetate/silver nanoparticles (AgNP) ultrafiltration membranes were correlated with their integral asymmetric porous structures, emphasizing the distinct features of each side of the membranes, that is, the active and porous layers surfaces. Composite membranes were prepared from casting solutions incorporating polyvinylpyrrolidone-covered AgNP using the phase inversion technique. The variation of the ratio acetone/formamide and the AgNP content resulted in a wide range of asymmetric porous structures with different hydraulic permeabilities. Comprehensive studies assessing the antibacterial activity against Escherichia coli (cell death and growth inhibition of bacteria in water) were performed on both membrane surfaces and in E. coli suspensions. The results were correlated with the surface chemical composition assessed by XPS. The silver-free membranes presented a generalized growth of E. coli , which is in contrast with the inhibition patterns displayed by the membranes containing AgNP. For the surface bactericide test, the growth inhibition depends on the accessibility of E. coli to the silver present in the membrane; as the XPS results show, the more permeable membranes (CA30 and CA34 series) have higher silver signal detected by XPS, which is correlated with a higher growth inhibition. On the other hand, the inhibition action is independent of the membrane porous structure when the membrane is deeply immersed in an E. coli inoculated suspension, presenting almost complete growth inhibition.

The purpose of this study was to calculate the effects of exercise programs on phase angle (PhA) in older people. A systematic review was undertaken in multiple electronic databases in accordance with the Preferred Reporting Items for Systematic Reviews and Meta-analyses statement guidelines for the purposes of selecting randomized controlled trials that measured the effects of the exercise programs on PhA in older adults on 31 March 2022. We carried out a random-effect meta-analysis for the effects of exercise programs on PhA. Additionally, we analysed the differences between subgroups in terms of weekly frequency, number of sets and repetitions, and duration of interventions. Studies were methodological assessed through the PEDro scale where one had excellent, ten had good, and three had poor methodological quality. For the purposes of the study, fourteen studies met the criteria for inclusion. However, four studies did not have enough information to be included in the quantitative analysis. The remaining ten articles revealed moderate effects on PhA in favour of intervention groups (p=0.009, SMD=0.72 [0.46-0.99], I 2 =54%). The meta-analysis also showed that interventions lasting twelve weeks are more successful in generating positive effects on PhA as opposed to eight weeks (SMD's=0.79 vs. 0.64, respectively). These results indicate that resistance training (RT) is an effective and safe to improve PhA in the older people, especially through RT programs lasting from eight to twelve weeks. A novel finding of this study was that RT is the most used type of exercise by authors when assessing the PhA in older adults., Competing Interests: Declaration of Competing Interest The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Elsevier B.V. All rights reserved.)

(1) Background: we aimed to describe the disease-specific quality of life (QoL) of ischemic stroke patients treated with acute revascularization therapy, its evolution from 6 months to 12 months, and associated factors. (2) Methods: QoL was assessed with the SS-QoL in consecutive patients treated with either intravenous thrombolysis (IVT) and/or mechanical thrombectomy (MT). Variables associated with QoL scores and its evolution were studied using multivariate mixed models, and interaction with time. Analyses were performed in four domains of SS-QoL: self-care, mobility, mood, and social roles. (3) Results: Among the 501 included patients (mean (sd) age 68.9 (14.5), 49% women), lower post-stroke QoL was independently related to lower level of school education, prestroke mRS > 2, and 24 h NIHSS score > 4. Independent predictors of unfavorable evolution of QoL over time were age <75 years (Mobility p = 0.0194 and Mood p = 0.0015), NIHSS score ≤ 4, (Self-care p = 0.0053 and Mood p = 0.0048), and modified Rankin Scale score ≤ 2 (Social roles, p = 0.0006). Revascularization therapy had no significant effect on the QoL scores, but patients treated with MT (alone or as bridging therapy) had significantly greater improvement in mobility score between 6 and 12 months than patients treated with IVT alone (p = 0.0072). (4) Conclusion: QoL evolution over one year had only slight variation and was associated with the modalities of acute treatment, age, and stroke severity.

We hypothesized that dietary inclusion of 15% Laminaria digitata , supplemented or not with carbohydrases, could improve the nutritional value of poultry meat without impairing animal growth performance. A total of 120 22-day old broilers were fed the following dietary treatments ( n = 10) for 14 days: cereal-based diet (control); control diet with 15% L. digitata (LA); LA diet with 0.005% Rovabio ® Excel AP (LAR); LA diet with 0.01% alginate lyase (LAE). Final body weight was lower and feed conversion ratio higher with LA diet than with the control. The ileal viscosity increased with LA and LAR diets relative to control but without differences between LAE and control. The pH of thigh meat was higher, and the redness value of breast was lower with LA diet than with control. Meat overall acceptability was positively scored for all treatments. The γ-tocopherol decreased, whereas total chlorophylls and carotenoids increased in meat with alga diets relative to control. The percentage of n-3 polyunsaturated fatty acids (PUFA) and accumulation of bromine and iodine in meat increased with alga diets compared with control. Feeding 15% of L. digitata to broilers impaired growth performance but enhanced meat quality by increasing antioxidant pigments, with beneficial effects on n-3 PUFA and iodine.

The transformation of biomass, a carbon resource presenting a huge potential to produce valuable chemicals, requires the search for sustainable catalytic routes. This work proposes the microwave-assisted oxidation of biomass -derived substrates, such as glycerol and the furfural derivatives 5-(hydroxymethyl)furfural (HMF) and 5-hydroxymethyl-2-furancarboxylic acid (HFCA), using the C-scorpionate dichloro-gold(III) complex [AuCl 2 (κ 2 -Tpm)]Cl (Tpm = HCpz 3 ; pz = pyrazol-1-yl) as a catalyst, as prepared and supported on graphene, in solvent-free conditions. The unprecedented application of a mechanochemical procedure (in a planetary ball mill, in solid state) to synthesize a C-scorpionate complex, the [AuCl 2 (κ 2 -Tpm)]Cl, is disclosed. The immobilization of [AuCl 2 (κ 2 -Tpm)]Cl on graphene was performed using different methods, including some (e.g., microwave irradiation and liquid assisted grinding) for the first time. The structural properties and the performance of the prepared catalytic materials are presented and discussed.

The growing threat of emerging waterborne contaminants is a global concern, fuelled in part by the ineffectiveness of current remediation strategies. One of the most prominent remediation strategies is catalytic photodegradation, particularly with TiO 2 nanoparticles (NPs), but its full utilization is hampered by using only UV radiation, which is scarce in sunlight. To fully benefit from the sunlight abundance, several efforts are focused on the tailoring of TiO 2 to make it more active in visible (Vis) light. However, this target is yet to be met, sought for new developments. In a recent research paper entitled " Visible light-driven photodegradation of triclosan and antimicrobial activity against Legionella pneumophila with cobalt and nitrogen co-doped TiO 2 anatase nanoparticles" [ 1 ], we investigated the co-doping potential of cobalt and nitrogen in TiO 2 NPs for water decontamination, focusing on its application for the degradation of triclosan (TCS) under Vis LED light irradiation. Herein, the synthesis methodology for the preparation of doped TiO 2 with nitrogen is described in detail, along with complementary data on the characterisation of all previously synthesised photocatalysts in the form of specific surface area determination (B.E.T. method) based on the obtained physisorption isotherms, X-ray photoelectron spectroscopy (XPS), and the automatic determination of bandgap energy through the diffuse reflectance spectra (DRS) analysis by using the GapExtractor© software. This dataset article also includes optimised photocatalytic reaction conditions, specifically conducted under monochromatic LED light irradiation. The employed LED irradiation conditions can support photocatalytic research in the field, since LED systems are costless and have a long-life span compared to most conventional UV-Vis systems. In addition, raw UV-Vis spectra and high-performance liquid chromatography (HPLC) chromatograms for monitoring the TCS degradation reaction are also included, as are powder X-ray diffractograms (XRD) of recycled doped-TiO 2 photocatalysts, confirming the renewable efficiency of the synthesised photocatalysts to pursue green chemistry principles., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2021 The Authors.)

Dielectric properties and spectral dependence of the photocatalytic constant of Co doped P25 Degussa powder were studied. Doping of TiO 2 matrix with cobalt was achieved by precipitation method using of Tris(diethylditiocarbamate)Co(III) precursor (CoDtc-Co[(C 2 H 5 ) 2 NCS 2 ] 3 ). Five different Co contents with nominal Co/Ti atomic ratios of 0.005, 0.01, 0.02, 0.05 and 0.10 were chosen. Along with TiO 2 :Co samples, a few samples of nanopowders prepared by Sol-Gel method were also studied. As it follows from XPS and NMR studies, there is a concentration limit (TiO 2 :0.1Co) where cobalt atoms can be uniformly distributed across the TiO 2 matrix before metallic clusters start to form. It was also shown that CoTiO 3 phases are formed during annealing at high temperatures. From the temperature dependence of the dielectric constant it can be concluded that the relaxation processes still take place even at temperatures below 400 °C and that oxygen defect Ti-O octahedron reorientation take place at higher temperatures. The spectral dependency of the photocatalytic constant reveals the presence of some electronic states inside the energy gap of TiO 2 for all nanopowdered samples.

Cotton fabrics decorated with Cu 2 O-Ag and Cu 2 O-Ag-AgBr NPs have been prepared using chemically immobilized Cu 2 O NPs as sacrificial templates. The objective is to prepare Cu 2 O-Ag heterostructures with Ag being intimately in contact with Cu 2 O NPs by galvanic replacement reactions without addition of any external reducing agent. Field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis were used to study the morphology and the chemical composition of the nanocomposites formed on the fabrics. The morphology of the ensuing nanostructures was shown to be dependent on the Ag precursor, AgNO 3 , concentration. The antimicrobial activity of the treated fabrics was evaluated against Staphylococcus aureus and Escherichia coli as model strains of gram-negative and gram-positive, respectively. The results showed that the fabrics loaded with Cu 2 O-Ag and Cu 2 O-Ag-AgBr nanocomposites exhibited enhanced sterilization activity compared to the Cu 2 O treated fabric., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The conchocelis life cycle stage of P. dioica represents an unexplored source of bioactive compounds. The aim of this study was to generate and characterise, for the first time, hydrolysates of conchocelis using a specific combination of proteases (Prolyve ® and Flavourzyme ® ). Hydrolysate molecular mass distribution and free amino acid contents were assessed, and the antioxidant activity was determined using a range of in vitro assays. The protein content and the total amino acid profiles of conchocelis were also studied. Conchocelis contained ~25% of protein (dry weight basis) and had a complete profile of essential amino acids. Direct sequential enzymatic treatment modified the profile of the generated compounds, increasing the amount of low molecular weight peptides (<1 kDa). There was a significant improvement in the antioxidant activity of the hydrolysates compared with the control (up to 2.5-fold), indicating their potential as a novel source of antioxidant ingredients.

In this study, cotton fabrics decorated with Ag/AgCl and Ag/AgBr NPs were produced by a simple hydrothermal treatment using AgCl and AgBr as precursors. Their morphological features as well as, chemical composition and structural and luminescence properties were compared. Their water disinfection aptitude against E. coli and S. aureus was also investigated under solar illumination in batch as well asin dynamic conditions. The highest activity was observed for Cot-Ag/AgCl with a quasi-complete inactivation of E. coli and S. aureus(1.5 × 10 7 cfu mL -1 ) within 15 min illumination. Disinfection efficiency under continuous flow was also tested using a home-made photoreactor and the cotton fabrics with the most efficient photocatalyst (Ag/AgCl). It has shown to be efficient at least for 10 cycles revealing the robustness of the functionalization. The mechanism of photocatalytic disinfection was explained in terms of the surface plasmon resonance (SPR) induced by the presence of Ag NPs, the resulting holes, h + , being one of the most intervenient species in the disinfection mechanism. The difference in the photocatalytic efficiency between AgCl and AgBr functionalized cotton was attributed to differences in the carriers (h + and e-) lifetime. This work provides a proof of concept for the potential applicability of Cot-Ag/AgCl or Cot-Ag/AgBr for in-flow potabilization of water under solar illumination., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Loosening of orthodontic and orthopedic implants is a critical and common clinical problem. To minimize the numbers of revision surgeries due to peri-implant inflammation or insufficient osseointegration, developments of new implant manufacturing strategies are indicated. Ultrafast laser surface texturing is a promising contact-free technology to modify the physicochemical properties of surfaces toward an anti-infectious functionalization. This work aims to texture Ti6Al4V surfaces with ultraviolet (UV) and green (GR) radiation for the manufacturing of laser-induced periodic surface structures (LIPSS). The assessment of these surface modifications addresses key aspects of topography, morphology and chemical composition. Human primary mesenchymal stromal cells (hMSCs) were cultured on laser-textured and polished Ti6Al4V to characterize the surfaces in terms of their in vitro biocompatibility, cytotoxicity, and metal release. The outcomes of the in vitro experiment show the successful culture of hMSCs on textured Ti6Al4V surfaces developed within this work. Cells cultured on LIPSS surfaces were not compromised in terms of their viability if compared to polished surfaces. Yet, the hMSC culture on UV-LIPSS show significantly lower lactate dehydrogenase and titanium release into the supernatant compared to polished. Thus, the presented surface modification can be a promising approach for future applications in orthodontics and orthopedics.

An experimental and theoretical investigation on microwave plasma-based synthesis of free-standing N-graphene, i.e., nitrogen-doped graphene, was further extended using ethanol and nitrogen gas as precursors. The in situ assembly of N-graphene is a single-step method, based on the introduction of N-containing precursor together with carbon precursor in the reactive microwave plasma environment at atmospheric pressure conditions. A previously developed theoretical model was updated to account for the new reactor geometry and the nitrogen precursor employed. The theoretical predictions of the model are in good agreement with all experimental data and assist in deeper understanding of the complicated physical and chemical process in microwave plasma. Optical Emission Spectroscopy was used to detect the emission of plasma-generated ''building units'' and to determine the gas temperature. The outlet gas was analyzed by Fourier-Transform Infrared Spectroscopy to detect the generated gaseous by-products. The synthesized N-graphene was characterized by Scanning Electron Microscopy, Raman, and X-ray photoelectron spectroscopies.

The presence of a biomimetic HAP coating on titanium surface, which reduces the structural stiffness, is essential to improve implants biocompatibility and osteointegration. In this study, new citrate-HAP (cHAP) coatings were produced by a simple hydrothermal method on pure titanium (Ti) surface, without requiring any additional pretreatment on this metal surface. The formed cHAP coatings consisting of nanorod-like hydroxyapatite particles, conferred nanoroughness and wettability able to endow improved biological responses. Indeed, the presence of citrate species in the precipitate medium seems to be responsible for controlling the morphology of the new coatings. The presence of citrate groups on the surface of cHAP coatings, identified by chemical composition analysis, due to their implication in bone metabolism can additionally bring an add-value for bone implant applications. From a mechanical point of view, the Finite Element algorithm showing that cHAP coatings tend to decrease the mechanical stress at pure Ti, further favors these new coatings applicability. Overall, the simple and expedite strategy used to developed new biomimetic coatings of citrate-HAP resulted in improved physicochemical, morphological and mechanical properties of Ti, which can endeavor improved implantable materials in bone healing surgical procedures., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Objective: Over half of pregnant women in India are affected by anaemia, which can lead to premature birth, low birth weight and maternal and child mortality. Using formative research, we aimed to understand social and cultural factors around iron and folic acid (IFA) supplement provision and adherence to identify potential strategies for improving adherence and behaviours to prevent and treat anaemia among pregnant and lactating Indian women., Design: In-depth interviews and focus group discussions with women and key informant interviews with health officials and workers., Setting: Four districts in two Indian states: Allahabad and Bara Banki districts in Uttar Pradesh and Chikkballapura and Mandya districts in Karnataka., Participants: Pregnant and lactating women (n 65) and district officials and community health workers (n 14)., Results: Most women were aware of anaemia but did not understand its seriousness and consequences. All women received IFA supplements (predominantly for free), but many were not adherent because of side effects; lack of information from healthcare providers on the causes of anaemia, its seriousness and solutions and low social support. To address anaemia, women were most confident in their ability to prepare and eat healthier foods but lacked control over resources such as appropriate food availability., Conclusions: Based on the findings, we recommend multicomponent interventions to train healthcare providers, address systemic barriers and involve family members to support IFA supplement adherence and dietary changes. Future research will determine which strategies are most effective to reduce the burden of anaemia in India among pregnant and lactating women.

The composition and architecture of a scaffold determine its supportive role in tissue regeneration. In this work, we demonstrate the feasibility of obtaining a porous electrospun fibrous structure from biodegradable polyurethanes (Pus) synthesized using polycaprolactone-diol as soft segment and, as chain extenders, chitosan (CS) and/or dimethylol propionic acid. Fourier transform infrared spectroscopy and proton nuclear magnetic resonance confirmed the syntheses. Fibre mats' properties were analysed and compared with those of solvent cast films. Scanning electron microscopy images of the electrospun scaffolds revealed fibres with diameters around 1 μm. From tensile tests, we found that Young's modulus increases with CS content and is higher for films (2.5 MPa to 6.5 MPa) than for the corresponding fibre mats (0.8 MPa to 3.2 MPa). The use of CS as the only chain extender improves recovery ratio and resilience. From X-ray diffraction, a higher crystalline degree was identified in fibre mats than in the corresponding films. Films' wettability was enhanced by the presence of CS as shown by the decrease of water contact angle. X-ray photoelectron spectroscopy revealed that while ester groups are predominant at the films' surface, ester and urethanes are present in similar concentrations at fibres' surface, favouring the interaction with water molecules. Both films and fibres undergo hydrolytic degradation. In vitro evaluation was performed with human dermal fibroblasts. No PU sample revealed cytotoxicity. Cells adhered to fibre mats better than to films and proliferation was observed only for samples of CS-containing PUs. Results suggest that electrospun fibres of CS-based polyurethanes are good candidate scaffolds for soft tissue engineering., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Hydroxide [Ag(OH)L] (L = IV L, V L, VI L, VII L), oxide [{AgL} 2 }(μ-O)] (L = I L, II L, III L, V L, VI L) or chloride [Ag II L]Cl, [Ag( VI L) 2 ]Cl complexes were obtained from reactions of mono- or bicamphorimine derivatives with Ag(OAc) or AgCl. The new complexes were characterized by spectroscopic (NMR, FTIR) and elemental analysis. X-ray photoelectron spectroscopy (XPS), ESI mass spectra and conductivity measurements were undertaken to corroborate formulations. The antimicrobial activity of complexes and some ligands were evaluated towards Candida albicans and Candida glabrata , and strains of the bacterial species Escherichia coli , Burkholderia contaminans , Pseudomonas aeruginosa and Staphylococcus aureus based on the Minimum Inhibitory Concentrations (MIC). Complexes displayed very high activity against the Candida species studied with the lowest MIC values (3.9 µg/mL) being observed for complexes 9 and 10A against C. albicans . A significant feature of these redesigned complexes is their ability to sensitize C. albicans , a trait that was not found for the previously investigated [Ag(NO 3 )L] complexes. The MIC values of the complexes towards bacteria were in the range of those of [Ag(NO 3 )L] and well above those of the precursors Ag(OAc) or AgCl. The activity of the complexes towards normal fibroblasts V79 was evaluated by the MTT (3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide) assay. Results showed that the complexes have a significant cytotoxicity.

In this work, cellulose films pre-activated with carbonyldiimidazole (CDI) and grafted with 1,6-hexanediamine, were decorated with silver nanoparticles (AgNPs). The generation of AgNPs was followed by quartz crystal microbalance (QCM). The obtained films were characterized by X-Ray Photoelectron Spectroscopy (XPS) and imaged by atomic force microscopy (AFM). XPS confirmed the synthesis in situ of AgNPs on the film attesting their oxidation state. The results from the three techniques were compared showing how sound the quantitative treatment of the results issued from these techniques can be. The main objective of this work is exactly to show that the quantitative exploration of the results of different characterization techniques can and should be practiced systematically instead of just comparing them qualitatively.

A highly hydrophilic carbon nanomaterial was generated by using an electrochemical approach, and its structure, chemical composition, redox properties, antioxidant activity and effects on cells were characterised. It was found that the nanomaterial possesses a structure dominated by sp 2 carbon atoms in a non-ordered carbon network formed by small clusters (<2 nm) of a carbonaceous material. This material has an outstanding capability for donating electrons and an unusual ability to bind metal cations. Antioxidant activity assays showed that it displays a high scavenging activity against both 2,2-diphenyl-1-picrylhydrazyl and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) radicals, and a concentration-dependent ability to protect mitochondrial lipids and intracellular thiol groups from oxidation promoted by external oxidising agents. Cell-based assays also revealed that the nanomaterial has the ability to protect neuronal cells against oxidative damage and toxicity promoted by tert-butyl hydroperoxide and amyloid-β 1-42 peptide. These results, combined with the attractive methodology for generating this hydrophilic carbon-based nanomaterial, make this study the first step in addressing the therapeutic application of this new material., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Tuberculosis patients taking second line drugs such as ethionamide (ETH) have often experienced previous treatment failure and usually have a complex history of disease and treatment that can span decades. Mutations in the ETH activating enzyme, EthA, confer resistance through undescribed mechanisms. To explore the impact of EthA mutations on ETH resistance, data from a total of 160 ETH R isolates was analysed. The most frequently mutated positions are within regions that display sequence conservation with the active site of OTEMO, another FAD-containing NADH-binding Baeyer-Villiger monooxygenase (BVMO), or with the sugar binding site of galectin-4N. Additionally, to look at a possible role of EthR on ETH resistance we purified an EthR mutant identified in a clinical isolate, F110L, and found it to bind the ethA-ethR intergenic region with higher affinity than the wild type regulator in gel shift assays. The ability of cyclic di-GMP to enhance DNA binding is maintained in the EthR mutant. To our knowledge, this is the first ETH resistance study that combines sequence and resistance data of clinical isolates with functional and structural information., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Five silver camphor complexes of formulae [Ag 2 (L)(L') 2 ] (1,3,5) or [Ag(L) 2 (L')] (2,4) were synthesized from silver nitrate and the suitable camphor carboxylate (L 1 ) or camphor carboxamides (L 3 , L 4 ). The complexes were characterized by elemental analysis and spectroscopic techniques (NMR, FTIR, XPS). Computational calculations support coordination of the carboxylate group to silver, in the case of complex 2 and combined mixed keto/carboxylate in the case of complex 1. The stability of the complexes highly relies on the tetrahedral geometry of the lithium ion that binds to four oxygen atoms of the camphor carboxylate ligands. The redox properties of complexes 1 and 4 studied by cyclic voltammetry confirm the facile reduction of the metal sites that depending on the experimental conditions may lead to formation of silver nanoparticles as confirmed by XPS and TEM. Complexes 1, 2 and 4 were tested for cytotoxic activities against A2780 (IC 50 , 11-14 μM) and A2780 cisplatin resistant (A2780cisR) (IC 50 , 4-7 μM) cells using the MTT assay. The result showed that the complexes have anticancer activity higher than cisplatin. Complex 1 was also probed for cytotoxicity against the non-tumoral human embryonic kidney (HEK 293, IC 50 , 62.2 ± 16 μM) cells showing low toxicity in agreement with the silver camphor carboxylate complexes having a considerable selectivity for the ovarian cancer cells A2780 and cisplatin resistant A2780cisR which is a key point under pharmacological uses., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Thin films of chitosan (CS) coated on glass substrates were used as support for the immobilization of nanostructures TiO 2 /ZnS via a mild chemical process followed by a hydrothermal treatment at 90 °C. The preparation route involved the coating of the CS film on the glass substrate followed by the deposition of a thin layer of Ti(OBu) 4 precursor and immersion in a solution of Zn(O 2 CCH 3 ) 2 and Na 2 S. After a hydrothermal treatment at 90 °C, an even layer of TiO 2 anatase decorated by ZnS nanorods was generated. Evidence of the formation of TiO 2 anatase and ZnS was confirmed by XRD, Raman and XPS, and the morphology of the TiO 2 layer and ZnS nanoparticles was analyzed by FE-SEM observations. The photocatalytic activity of the CS-TiO 2 -ZnS systems was evaluated by the degradation of a wide range of organic compounds including aromatic amines and carboxylic acids under a conventional halogen lamp., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Direct assembling of N-graphene, i.e. nitrogen doped graphene, in a controllable manner was achieved using microwave plasmas at atmospheric pressure conditions. The synthesis is accomplished via a single step using ethanol and ammonia as carbon and nitrogen precursors. Tailoring of the high-energy density plasma environment results in a selective synthesis of N-graphene (~0.4% doping level) in a narrow range of externally controlled operational conditions, i.e. precursor and background gas fluxes, plasma reactor design and microwave power. Applying infrared (IR) and ultraviolet (UV) irradiation to the flow of free-standing sheets in the post-plasma zone carries out changes in the percentage of sp 2 , the N doping type and the oxygen functionalities. X-ray photoelectron spectroscopy (XPS) revealed the relative extension of the graphene sheets π-system and the type of nitrogen chemical functions present in the lattice structure. Scanning Electron microscopy (SEM), Transmission Electron microscopy (TEM) and Raman spectroscopy were applied to determine morphological and structural characteristics of the sheets. Optical emission and FT-IR spectroscopy were applied for characterization of the high-energy density plasma environment and outlet gas stream. Electrochemical measurements were also performed to elucidate the electrochemical behavior of NG for supercapacitor applications.

The effect of microwave and mechanochemical ball milling energy inputs was studied for the peroxidative oxidation (with aqueous H2O2) of cyclohexane to cyclohexanol and cyclohexanone, over CoCl2 and/or V2O5 dispersed (μm scale) catalysts. A maximum total yield of cyclohexanol and cyclohexanone of 43% after 1 h of reaction at 30 °C, in acetonitrile and under microwave irradiation (5 W), was achieved over the CoCl2-V2O5 (3 : 1) catalyst prepared by ball milling. Cyclohexanol is the main final product with a selectivity of up to 93% over cyclohexanone. Conducting the oxidation reaction under microwave irradiation under the same conditions but without any mechanochemical treatment of the catalyst prior to use resulted in a lower total yield of 30% with a lower selectivity (69%) towards cyclohexanol over cyclohexanone. The sole application of mechanochemical treatment for the catalyst preparation and the catalytic oxidation of cyclohexane allowed to reach yields of 29% after 1 h of reaction, at room temperature, without microwave irradiation and any additive and in the absence of any organic solvent. Ball milling is shown to provide a convenient, solvent-free method to disperse these solid catalysts and to promote the above cyclohexane oxidation, although, in the latter case, not so effectively as microwave irradiation.

Porphyra dioica is a commercial seaweed consumed all over the world, mostly in the shape of nori sheets used for "sushi" preparation. It is a well-known part of the Asian diet with health benefits, which have been associated, among others, to the high levels of n -3 and n- 6 fatty acids in this red alga. However, other highly valued lipids of Porphyra are polar lipids that remain largely undescribed and can have both nutritional value and bioactivity, thus could contribute to the valorization of this seaweed. In this context, the present work aims to identify the lipidome of two life cycle stages of the Atlantic species Porphyra dioica : the early life stage conchocelis produced in an indoor-nursery, and young blades produced outdoors using an integrated multitrophic aquaculture (IMTA) framework. Both the blades (gametophyte) and conchocelis (sporophyte) are commercialized in the food and cosmetics sectors. Liquid chromatography coupled to Q-Exactive high resolution-mass spectrometry (MS) platform was used to gain insight into the lipidome of these species. Our results allowed the identification of 110 and 100 lipid molecular species in the lipidome of the blade and conchocelis, respectively. These lipid molecular species were distributed as follows (blade/conchocelis): 14/15 glycolipids (GLs), 93/79 phospholipids (PLs), and 3/6 betaine lipids. Both life stages displayed a similar profile of GLs and comprised 20:4( n -6) and 20:5( n -3) fatty acids that contribute to n -3 and n -6 fatty acid pool recorded and rank among the molecular species with higher potential bioactivity. PLs' profile was different between the two life stages surveyed, mainly due to the number and relative abundance of molecular species. This finding suggests that differences between both life stages were more likely related with shifts in the lipids of extraplastidial membranes rather than in plastidial membranes. PLs contained n -6 and n -3 precursors and in both life stages of Porphyra dioica the n -6/ n -3 ratio recorded was less than 2, highlighting the potential benefits of using these life stages in human diet to prevent chronic diseases. Atherogenic and thrombogenic indexes of blades (0.85 and 0.49, respectively) and conchocelis (0.34 and 0.30, respectively) are much lower than those reported for other Rhodophyta, which highlights their potential application as food or as functional ingredients. Overall, MS-based platforms represent a powerful tool to characterize lipid metabolism and target lipids along different life stages of algal species displaying complex life cycles (such as Porphyra dioica ), contributing to their biotechnological application., Competing Interests: The authors declare no conflict of interest.

In the present work, a simple, reliable and cost-effective approach to functionalize cotton fabrics with Ag-TiO 2 nanoparticles strongly bound to the fibres and with visible-light-responsive photo-activity is presented. The hybrid cotton-Ag-TiO 2 fabrics were characterized by Raman, AFM, FE-SEM, TGA, XPS GSDR, and LIL to confirm the generation of metallic Ag nanoparticles and crystalline TiO 2 and investigate how the concentration of Ag and TiO 2 precursors affected the morphology and the luminescence properties of the nanostructured layer grafted on the cotton fibres. The photocatalytic activity of the cotton-Ag-TiO 2 hybrid systems was evaluated by the discoloration of Remazol Brilliant Blue R in water under a xenon lamp irradiation (sunlight simulator) equipped with selective filters. The extended photocatalytic activity to the visible is here explained by a synergistic effect of both the excitation of the Ag NPs plasmon resonance by visible light and a delayed electron-hole recombination rate caused by Ag NPs, as it can be observed by UV absorption., (Copyright © 2017 Elsevier Inc. All rights reserved.)

A simple approach to functionalize cotton fabrics with Au and TiO 2 nanostructured layer is presented. Hybrid fabrics (Cot-Au-TiO 2 ) are prepared through reduction of AuCl 4 - on cotton, followed by a non-aqueous sol-gel procedure using tetrabutyltitanate and a hydrothermal treatment at 110°C. The generation of crystalline TiO 2 is confirmed by Raman spectroscopy. The fibres morphology and their roughness are characterized by AFM and FE-SEM. XPS shows how the concentration of the NPs precursors (Au and TiO 2 ) affects the layer composition. GSDR (Ground State Diffuse Reflectance Absorption Spectroscopy) and LIL (Laser induced luminescence) reveal a strong quenching effect induced by Au NPs. Photocatalytic activity measured through the Remazol Blue (RB) degradation reveals an enhancement under visible light, which increases with Au loading. This strong enhancement is explained through the surface plasmon resonance brought by Au NPs., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Macroalgae have been seen as an alternative source of molecules with promising bioactivities to use in the prevention and treatment of current lifestyle diseases. In this vein, the lipophilic fraction of short-term (three weeks) cultivated Bifurcaria bifurcata was characterized in detail by gas chromatography-mass spectrometry (GC-MS). B. bifurcata dichloromethane extract was composed mainly by diterpenes (1892.78 ± 133.97 mg kg -1 dry weight (DW)), followed by fatty acids, both saturated (550.35 ± 15.67 mg kg -1 DW) and unsaturated (397.06 ± 18.44 mg kg -1 DW). Considerable amounts of sterols, namely fucosterol (317.68 ± 26.11 mg kg -1 DW) were also found. In vitro tests demonstrated that the B. bifurcata lipophilic extract show antioxidant, anti-inflammatory and antibacterial activities (against both Gram-positive and Gram-negative bacteria), using low extract concentrations (in the order of µg mL -1 ). Enhancement of antibiotic activity of drug families of major clinical importance was observed by the use of B. bifurcata extract. This enhancement of antibiotic activity depends on the microbial strain and on the antibiotic. This work represents the first detailed phytochemical study of the lipophilic extract of B. bifurcata and is, therefore, an important contribution for the valorization of B. bifurcata macroalgae, with promising applications in functional foods, nutraceutical, cosmetic and biomedical fields., Competing Interests: The authors declare no conflict of interest. The funding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the decision to publish the results.

Resistive switching in metal-insulator-metal nanosctructures is being intensively studied for nonvolatile memory applications. Here, we report unipolar resistive switching in Pt/MgO/Ta/Ru structures, with a 30 nm oxide barrier. A forming process was needed to initiate the resistive switching, which was then observed for all Set and Reset voltage polarity combinations. We studied the influence of the voltage polarity on the variability of the Set/Reset voltages and ON/OFF resistances and revealed the importance of a thin TaO x layer working as an oxygen revervoir for resistive switching. The mechanism behind this phenomenon can be understood in terms of conductive filaments formation/rupture with a contribution from Joule heating. Resistance change is thus caused by a voltage-driven oxygen vacancy motion in the MgO layer and a filament model was proposed for each polarity mode. A OFF/ON resistance ratio of at least 2 orders of magnitude was obtained with resistive states stable up to 10 4 s. Our results open the prospect to improve switching performance in other resistive switching systems, by proving a better understanding of the differences between operation modes.

The lipidome of the red seaweed Gracilaria sp., cultivated on land-based integrated multitrophic aquaculture (IMTA) system, was assessed for the first time using hydrophilic interaction liquid chromatography-mass spectrometry and tandem mass spectrometry (HILIC-MS and MS/MS). One hundred and forty-seven molecular species were identified in the lipidome of the Gracilaria genus and distributed between the glycolipids classes monogalactosyl diacylglyceride (MGDG), digalactosyl diacylglyceride (DGDG), sulfoquinovosyl monoacylglyceride (SQMG), sulfoquinovosyl diacylglyceride (SQDG), the phospholipids phosphatidylcholine (PC), lyso-PC, phosphatidylglycerol (PG), lyso-PG, phosphatidylinositol (PI), phosphatidylethanolamine (PE), phosphatic acid (PA), inositolphosphoceramide (IPC), and betaine lipids monoacylglyceryl- and diacylglyceryl- N,N,N -trimethyl homoserine (MGTS and DGTS). Antiproliferative and anti-inflammatory effects promoted by lipid extract of Gracilaria sp. were evaluated by monitoring cell viability in human cancer lines and by using murine macrophages, respectively. The lipid extract decreased cell viability of human T-47D breast cancer cells and of 5637 human bladder cancer cells (estimated half-maximal inhibitory concentration (IC 50 ) of 12.2 μg/mL and 12.9 μg/mL, respectively) and inhibited the production of nitric oxide (NO) evoked by the Toll-like receptor 4 agonist lipopolysaccharide (LPS) on the macrophage cell line RAW 264.7 (35% inhibition at a concentration of 100 μg/mL). These findings contribute to increase the ranking in the value-chain of Gracilaria sp. biomass cultivated under controlled conditions on IMTA systems.

A green, safe and fast procedure is presented for in situ generation of nanoparticles (NPs) of cuprous oxide (Cu2O) onto cotton fibres at room temperature using water as a solvent. The method is based on a mild surface oxidation of cellulose fibres to generate in a controlled way carboxylic groups acting as a binding site for the adsorption of Cu(2+) via electrostatic coordination. Then, the adsorbed Cu(2+) ions were readly converted into Cu2O by dipping the treated cotton fibres into a aqueous solution of a reducing agent. Field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), as well as UV-vis absorption and emission spectroscopic methods were used to analyse the size, morphology, chemical composition and the crystalline structure of the generated nanoparticles on the fabrics. The morphology of the ensuing Cu2O nanoparticles was shown to be dependent on the reduycing agent used. Antibacterial properties of the modified fibres were also investigated., (Published by Elsevier Ltd.)

Electrospun materials are promising scaffolds due to their light-weight, high surface-area and low-cost fabrication, however, such scaffolds are commonly obtained as ultrathin two-dimensional non-woven meshes, lacking on topographical specificity and surface side-dependent properties. Herein, it is reported the production of three-dimensional fibrous materials with an asymmetrical inner structure and engineered surfaces. The manufactured constructs evidence fibrous-based microsized conical protrusions [length: (10 ± 3) × 10(2) μm; width: (3.8 ± 0.8) × 10(2) μm] at their top side, with a median peak density of 73 peaks per cm(2), while their bottom side resembles to a non-woven mesh commonly observed in the fabrication of two-dimensional electrospun materials. Regarding their thickness (3.7 ± 0.1 mm) and asymmetric fibrous inner architecture, such materials avoid external liquid absorption while promoting internal liquid uptake. Nevertheless, such constructs also observed the high porosity (89.9%) and surface area (1.44 m(2) g(-1)) characteristic of traditional electrospun mats. Spray layer-by-layer assembly is used to effectively coat the structurally complex materials, allowing to complementary tailor features such as water vapor transmission, swelling ratio and bioactive agent release. Tested as wound dressings, the novel constructs are capable of withstanding (11.0 ± 0.3) × 10(4) kg m(-2) even after 14 days of hydration, while actively promote wound healing (90 ± 0.5% of wound closure within 48 hours) although avoiding cell adhesion on the dressings for a painless removal.

The adsorption of intact liposomes onto solid supports is a fundamental issue when preparing systems with encapsulated biological molecules. In this work, the adsorption kinetic of 1,2-dipalmitoyl-sn-glycero-3-[phospho-rac-(1-glycerol)] (sodium salt) liposomes onto cushions prepared from commom polyelectrolytes by the layer-by-layer technique was investigated with the main objective of finding the surface conditions leading to the adsorption of intact liposomes. For this purpose, different cushion surface roughnesses were obtained by changing the number of cushion bilayers. The adsorbed amount per unit area was measured through quartz crystal microbalance, surface morphology was characterized by atomic force microscopy, and the surface composition was assessed by X-ray photoelectron spectroscopy. The results show that (1) the amount of adsorbed lipids depends on the number of cushion bilayers, (2) the cushions are uniformly covered by the adsorbed lipids, and (3) the surface morphology of polymer cushions tunes liposome rupture and its adsorption kinetics. The fraction of ruptured liposomes, calculated from the measured amount of adsorbed lipids, is a function of surface roughness together with other surface morphology parameters, namely the dominating in-plane spatial feature size, the fractal dimension, and other textural features as well as amplitude and hybrid parameters.

This work stresses on damage at the molecular level caused by ultraviolet radiation (UV) in the range from 3.5 to 8 eV, deoxyribonucleic acid (DNA) films observed by X-ray photoelectron spectroscopy (XPS). Detailed quantitative XPS analysis, in which all the amounts are relative to sodium-assumed not to be released from the samples, of the carbon, oxygen, and particularly, nitrogen components, reveals that irradiation leads to sugar degradation with CO-based compounds release for energies above 6.9 eV and decrease of nitrogen groups which are not involved in hydrogen bonding at energies above 4.2 eV. Also the phosphate groups are seen to decrease to energies above 4.2 eV. Analysis of XPS spectra allowed to conclude that the damage on bases peripheral nitrogen atoms are following the damage on phosphates. It suggests that very low kinetic energy photoelectrons are ejected from the DNA bases, as a result of UV light induced breaking of the phosphate ester groups which forms a transient anion with resonance formation and whereby most of the nitrogen DNA peripheral groups are removed. The degree of ionization of DNA was observed to increase with radiation energy, indicating that the ionized phosphate groups are kept unchanged. This result was interpreted by the shielding of phosphate groups caused by water molecules hydration near sodium atoms.

In this work, we report the preparation of ultrathin submicro- and nanoporous cellulose films onto Si (100). The effect of different experimental conditions of preparation on the film surface morphology was studied, namely the role of the film casting method (spin- versus dip-coating), solvent (toluene or tetrahydrofuran), substrate pretreatment (hydrophilicity degree), and regeneration procedure with HCl vapors (two consecutive dips followed by regeneration or regeneration after each dip). The surface morphological structures presented in this work were never obtained before without the use of templates. A rather regular two-dimensional pore network was obtained onto the less hydrophilic Si substrate (contact angle≅68°), after two consecutive dips (with an intercalary rotation of 180º) in trimethylsilyl cellulose diluted in toluene and regeneration at the end. All the surfaces were characterized by atomic force microscopy.

Aim: The aim of the present work was to investigate ultrafast laser surface texturing as a surface treatment of Ti-6Al-4V alloy dental and orthopedic implants to improve osteoblastic commitment of human mesenchymal stem cells (hMSCs)., Materials & Methods: Surface texturing was carried out by direct writing with an Yb:KYW chirped-pulse regenerative amplification laser system with a central wavelength of 1030 nm and a pulse duration of 500 fs. The surface topography and chemical composition were investigated by scanning electron microscopy and x-ray photoelectron spectroscopy, respectively. Three types of surface textures with potential interest to improve implant osseointegration can be produced by this method: laser-induced periodic surface structures (LIPSSs); nanopillars (NPs); and microcolumns covered with LIPSSs, forming a bimodal roughness distribution. The potential of the laser treatment in improving hMSC differentiation was assessed by in vitro study of hMSCs spreading, adhesion, elongation and differentiation using epifluorescence microscopy at different times after cell seeding, after specific stainings and immunostainings., Results: Cell area and focal adhesion area were lower on the laser-textured surfaces than on a polished reference surface. Obviously, the laser-textured surfaces have an impact on cell shape. Osteoblastic commitment was observed independently of the surface topography after 2 weeks of cell seeding. When the cells were cultured (after 4 weeks of seeding) in osteogenic medium, LIPSS- and NP- textured surfaces enhanced matrix mineralization and bone-like nodule formation as compared with polished and microcolumn-textured surfaces., Conclusion: The present work shows that surface nanotextures consisting of LIPSSs and NPs can, potentially, improve hMSC differentiation into an osteoblastic lineage.